JP6786337B2 - Method for producing transition metal compound, catalyst for olefin polymerization and olefin polymer - Google Patents

Description

The present invention is a transition metal compound having a specific structure useful as a catalyst or catalyst component for olefin polymerization (also referred to as a metallocene compound in the present invention), an olefin polymerization catalyst containing the transition metal compound, and an olefin using the catalyst. The present invention relates to a method for producing a polymer, particularly a method for producing an olefin polymer in which ethylene homopolymerization or ethylene and α-olefin copolymerization is performed.

The metallocene catalyst is composed of a transition metal atom and an organic compound called a ligand, and the structure of this ligand is changed in the position of the substituent and the steric electronic effect of the substituent in the polymerization reaction. The physical properties of the obtained polymer can be widely controlled. Then, in order to synthesize a characteristic polymer, many crosslinked metallocene compounds having a specific structure have been synthesized.

For example, Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 disclose an olefin polymerization catalyst composed of a transition metal complex having a ligand in which cyclopentadiene is crosslinked with two adjacent dimethylsilylenes and methylarmoxane. In Patent Documents 5 to 8, a method for synthesizing a transition metal complex having a ligand in which cyclopentadiene and inden are adjacently double-crosslinked with the same or different cross-linking groups, an olefin polymerization catalyst, and the obtained polyolefin. A method for controlling the stereoregularity and the positional regularity of the above is disclosed. Patent Documents 4 and 6 disclose a method for producing an ethylene-based polymer having a wide molecular weight distribution and long-chain branching.

However, it is generally known that the above-mentioned adjacent double-crosslinked metallocene complex tends to be inferior in terms of catalytic activity as compared with a single-crosslinked metallocene complex having a similar structure, and it is not under specific conditions. And not suitable for industrial use.

On the other hand, some attempts have been reported to reduce the degree of long-chain branching (LCB level) in polyethylene by introducing a specific substituent into the metallocene complex. For example, in Patent Documents 9 to 11, a specific hydrocarbon group is introduced into the cyclopentadienyl structural portion of the ligand, and in Patent Document 12, a specific terminal unsaturated hydrocarbon is introduced into the crosslinked structural portion of the ligand. A method for synthesizing a transition metal complex into which a group has been introduced and an olefin polymerization catalyst are disclosed. In addition, Non-Patent Document 4 reports on those details.

Special Table No. 7-505418 U.S. Pat. No. 5,708,101 Japanese Unexamined Patent Publication No. 11-322774 Japanese Unexamined Patent Publication No. 2003-105016 International Publication No. 1995/009172 Japanese Unexamined Patent Publication No. 8-020605 Japanese Unexamined Patent Publication No. 2000-256411 International Publication No. 2013/031779 Special Table No. 9-501707 Japanese Unexamined Patent Publication No. 2014-111769 International Publication No. 2009/045301 International Publication No. 2006/004709

Organometallics 1993, 12, 1931. Organometallics 1994, 13, 1688. J. Am. Chem. Soc. 1996, 118, 1188. Macromolecules 2010, 43, 8836.

In general, a low level of long chain branching degree (LCB level) is desirable in terms of resin strength for improving strength by increasing rigidity, but when used in film applications, the melt viscoelasticity, processability and transparency of the resin Decreases. Long chain branching (LCB) contained in polyethylene is desirable in order to improve foam stability during film blow molding and enhance the processability of the resin. Therefore, it is desirable to control LCB levels in polyethylene using metallocene catalysts.

Furthermore, in order to achieve further high activation of the catalyst, the synthesis of a metallocene complex (transition metal compound) having a novel structure is expected.

That is, an object of the present invention is a novel transition metal compound capable of improving the polymerization activity without significantly reducing the amount of long-chain branching (LCB) introduced, a catalyst for olefin polymerization using this transition metal compound, and this catalyst. An object of the present invention is to provide a method for producing an olefin polymer used.

As a result of diligent research to achieve the above object, the present inventors have found that it is very effective to introduce at least one specific substituent into the cyclopentadienyl structural moiety in the adjacent double crosslinked metallocene complex. The present invention has been completed. That is, the present invention is specified by the following matters.

[1] A transition metal compound represented by the following general formula [1].

(In the general formula [1],
M is a Group 4 transition metal atom of the periodic table,
n is an integer of 1 to 4 that satisfies the valence of M.
X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand or an isolated electron pair, and the anion ligand is a halogen-containing group, a silicon-containing group, or oxygen. It is a containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene-based divalent derivative group. They may be combined with each other to form a ring,
Q ¹ and Q ² are substituted hydrocarbon groups which may be silicon-containing group or a germanium-containing group, may be the same or different from each other,
R ^{1 to} R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, and may be the same or different from each other. Often, adjacent substituents may bond to each other to form a ring, with R ¹ and Q ¹ , R ⁶ and Q ¹ , R ³ and Q ² , and R ⁴ and Q ² bonding to each other to form a ring. However, at least one of R ^{1 to} R ⁶ may be a substituent represented by the following general formula [2] or a substituent represented by the following general formula [3]. )

(In the general formulas [2] and [3], m is an integer of 1 to 8.)

[2] The transition metal compound according to [1], wherein M is a zirconium atom or a hafnium atom.
[3] X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group as an anion ligand. When n is 2 or more, a plurality of Xs existing are the same. However, the transition metal compounds according to [1] or [2], which may be different or may be bonded to each other to form a ring.
[4] R ^{1 to} R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups or nitrogen-containing groups, which may be the same or different from each other, and are substituted adjacent to each other. The groups may be bonded to each other to form a ring, and R ¹ and Q ¹ , R ⁶ and Q ¹ , R ³ and Q ² , and R ⁴ and Q ² may be bonded to each other to form a ring. However, at least one of R ^{1 to} R ⁶ is described in any one of [1] to [3], which is a substituent represented by the general formula [2] or a substituent represented by the general formula [3]. Transition metal compounds.
[5] R ^{1 to} R ⁶ are hydrocarbon groups having hydrogen atoms or carbon atoms 1 to 20, and may be the same or different from each other, and adjacent substituents may be bonded to each other to form a ring. Often, R ¹ and Q ¹ , R ⁶ and Q ¹ , R ³ and Q ² , R ⁴ and Q ² may combine with each other to form a ring, provided that at least one of R ^{1 to} R ⁶ is , The transition metal compound according to [4], which is a substituent represented by the general formula [2] or a substituent represented by the general formula [3].
[6] The transition metal compound according to any one of [1] to [5], wherein at least one of R ^{1 to} R ⁶ is a substituent represented by the general formula [2].

[7] The transition metal compound according to any one of [1] to [6] represented by the following general formula [4].

(In the general formula [4],
M, X, n and ^R 1 to R ⁶ is an M in the general formula [1], X, and n and ^R 1 to R ⁶ the same,
Q ³ and Q ⁴ are carbon atom or a silicon atom may be the same or different,
R ^{7 to} R ¹⁰ are hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups or sulfur-containing groups, and may be the same or different from each other. Often, R ⁷ and R ⁸ and R ⁹ and R ¹⁰ may combine with each other to form a ring, R ⁷ and R ¹ , R ⁸ and R ⁶ , R ⁹ and R ³ , R ¹⁰ and R ⁴ May combine with each other to form a ring. )

[8] R ⁷ to R ¹⁰ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group or nitrogen-containing groups may be the same or different, and R ⁷ R ⁸ , R ⁹ and R ¹⁰ may be combined with each other to form an independent ring, and R ⁷ and R ¹ , R ⁸ and R ⁶ , R ⁹ and R ³ , and R ¹⁰ and R ⁴ may be combined with each other. The transition metal compound according to [7], which may be bonded to form a ring.
[9] R ^{7 to} R ¹⁰ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different from each other, and R ⁷ and R ⁸ and R ⁹ and R ¹⁰ are bonded to each other. R ⁷ and R ¹ , R ⁸ and R ⁶ , R ⁹ and R ³ , and R ¹⁰ and R ⁴ may be combined with each other to form a ring [8]. ] The transition metal compound according to.
[10] The transition metal compound according to any one of [7] to [9], wherein R ⁷ and R ⁸ are the same group, and R ⁹ and R ¹⁰ are the same group.
[11] The transition metal compound according to [10], wherein R ^7- Q ^3- R ⁸ and R ^9- Q ^4- R ¹⁰ are the same group.

[12] A catalyst for olefin polymerization, which comprises the transition metal compound [A] according to any one of [1] to [11].
[13] Furthermore
[B] (B-1) Organometallic compound,
2. The compound according to [12], which comprises at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with a transition metal compound [A] to form an ion pair. Olefin polymerization catalyst.

[14] A method for producing an olefin polymer, which comprises a step of polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to [12] or [13].
[15] The olefin polymer according to [14], wherein the step of polymerizing or copolymerizing an olefin is a step of polymerizing ethylene alone or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms. Production method.

In the present specification, the term "polymerization" is used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymer but also copolymer. Used in the sense.

According to the present invention, a novel transition metal compound capable of improving the polymerization activity without significantly reducing the amount of long-chain branching (LCB) introduced, a catalyst for olefin polymerization using this transition metal compound, and this catalyst are used. It is possible to provide a method for producing the olefin polymer which has been used. When the olefin polymerization catalyst containing the transition metal compound of the present invention is used, for example, when ethylene homopolymerization or copolymerization of ethylene and α-olefin is performed, the olefin polymerization activity is better than that of the conventional olefin polymerization catalyst. In addition, an ethylene homopolymer or copolymer can be obtained without significantly reducing the amount of LCB introduced. In the prior art, none of these can be satisfied at the same time. That is, according to the present invention, an olefin polymer having high market value and excellent molding processability can be produced with good polymerization activity.

<Transition metal compound [A ]
The transition metal compound [A] of the present invention is a compound represented by the general formula [1], and is preferably a compound represented by the general formula [4].

In the general formula [1], M is a transition metal atom of Group 4 of the periodic table, for example, a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, and particularly preferably a zirconium atom.

n is an integer of 1 to 4 satisfying the valence of M, preferably 1 or 2.

X is a neutral ligand capable of coordinating with a hydrogen atom, a halogen atom, a hydrocarbon group, an anion ligand or a lone electron pair. The anion ligand contains a halogen-containing group (H1), a silicon-containing group (Si1), an oxygen-containing group (O1), a sulfur-containing group (S1), a nitrogen-containing group (N1), a phosphorus-containing group (P), and a boron. It is a group (B), an aluminum-containing group (Al) or a conjugated diene-based divalent derivative group (DE). In particular, X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group as an anion ligand.

When n is 2 or more, a plurality of Xs may be the same or different from each other, or may be combined with each other to form a ring. Further, when a plurality of rings are present, they may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, but chlorine or bromine is preferable.

The hydrocarbon group is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, and a 1-heptyl group. Group, 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, Pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, siamil (1,2-dimethylpropyl) group, iso-hexyl (4-) Methylpentyl) group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 4,4-dimethylpentyl Linear or branched alkyl groups such as groups;

Vinyl group, allyl group, propenyl (propa-1-en-1-yl ) group , iso- propenyl (propa-1-en-2-yl ) group , arenyl (propa-1,2-dien-1-yl ) Group, porcine-3-en-1-yl group, crotyl (but-2-en-1-yl) group, porcine-3-en-2-yl group, metalryl (2-methylallyl) group, erythrenyl (buta-) 1,3-Dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3-methylbutan-3) -En-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methylbut-2-en-1-yl) group, etc. Linear or branched alkenyl groups or unsaturated double bond-containing groups;

Linear or branched alkynyl groups such as ethynyl group, propa-2-in-1-yl group, propargyl (propa-1-in-1-yl) group or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl (4-iso-propylbenzyl) group, 2,4,6- Aromatically containing linear or branched groups such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group. Alkyl group and unsaturated double bond-containing group;

Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, trill (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , Afferous substituted (aryl) groups such as naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group; and the like.

Among the hydrocarbon groups, methyl group, iso-butyl (2-methylpropyl) group, neopentyl (2,2-dimethylpropyl) group, siamil (1,2-dimethylpropyl) group, benzyl group, phenyl group, Trill (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group and cumenyl (iso-propylphenyl) group are preferable.

The halogen-containing group (H1) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Examples thereof include ethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion and the like. Of these, a pentafluorophenyl group is preferable.

The silicon-containing group (Si1) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, and a tert-butyldimethylsilyl group. , Tert-Butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, trimethylsilylmethyl group and the like. Of these, a trimethylsilylmethyl group is preferable.

The oxygen-containing group (O1) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, sec- Butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di- Methoxy-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, Examples thereof include periodate anion. Of these, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.

The sulfur-containing group (S1) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a mesyl (methanesulfonyl) group, a phenylsulfonyl group, a tosyl (p-toluenesulfonyl) group, and a triflate (trifluoromethanesulfonyl). Group, nonaflate (nonafluorobutanesulfonyl) group, mesylate (methanesulfonate) group, tosylate (p-toluenesulfonate) group, triflate (trifluoromethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, etc. be able to. Of these, a triflate (trifluoromethanesulfonate) group is preferable.

The nitrogen-containing group (N1) is not particularly limited as long as the effects of the present invention are exhibited, and for example, an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group and a diallylamino group. Examples thereof include a group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholic group, a pyrrolyl group, a bistrifurylimide group and the like. Of these, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.

The phosphorus-containing group (P) is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include hexafluorophosphate anions.

The boron-containing group (B) is not particularly limited as long as the effects of the present invention are exhibited, and for example, tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl)). ) Borate anion, (benzyl) (Tris (pentafluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is hydrogen, alkyl group, substituent) (Indicating an aryl group or a halogen atom which may have) can be mentioned.

The aluminum-containing group (Al) is not particularly limited as long as the effect of the present invention is exhibited, and is, for example, a (M-halogen atom-aluminum atom-hydrocarbon group) four-membered ring or (M-hydrocarbon group-aluminum). Atomic-hydrocarbon group) AlR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.) capable of forming a four-membered ring can be mentioned.

The conjugated diene-based divalent derivative group (DE) is not particularly limited as long as the effects of the present invention are exhibited, and for example, 1,3-butadienyl group, isoprenyl (2-methyl-1,3-butadienyl) group, piperylenyl. Examples thereof include a metallocyclopentene group such as a (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group and a cyclopentadienyl group.

The neutral ligand capable of coordinating with a lone electron pair is not particularly limited as long as the effect of the present invention is exhibited, and for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, triethylamine, and the like. Examples include amines such as diethylamine, heterocyclic compounds such as pyridine, picolin, lutidine, oxazoline, oxazole, thiazole, imidazole and thiophene, and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine and tri-tert-butylphosphine. Can be done.

Q ¹ and Q ² are substituted hydrocarbon groups which may be silicon-containing group or a germanium-containing group, may be the same or different from each other.

As the hydrocarbon group of the hydrocarbon group which may have a substituent, a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a cycloalkylene group and an alkylidene group is preferable.

Specific examples of the hydrocarbon group having 1 or more and 20 or less carbon atoms include alkylene groups such as methylene, ethylene, propylene and butylene;

Isopropyridene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methylbuta-3-emethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, Methylphenylmethylene, phenylmethylene, phenylbut-3-emethylene, diphenylmethylene, ditrilmethylene, methylnaphthylmethylene, dinaphthylmethylene, benzylphenylmethylene, dibenzylmethylene, 1-methylethylene, 1,2-dimethylethylene, 1 -Substituted alkylene groups such as ethyl-2-methylethylene;

Cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptilidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene ;

Examples thereof include an alkylidene group such as ethylidene, propylidene and butylidene.

Specific examples of the silicon-containing group include silylene, methylsilylene, dimethylsilylene, diethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylcilylene, and diphenylsilylene. , Ditrilcilylene, methylnaphthylsilylene, dinaphthylcilylene, cyclodimethylenesilylene, cyclotrimethylenecilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenecilylene, cycloheptamethylenecilylene, tetramethyldisylylene, etc. Be done. Of these, dimethylsilylene, dibutylsilylene, diphenylcilylene, cyclodimethylenesilylene, cyclotrimethylenecilylene, cyclotetramethylenesilylene, cyclopentamethylenecilylene, and tetramethyldisylylene are preferable.

Examples of the germanium-containing group include a group obtained by converting silicon into germanium in the specific example of the divalent silicon-containing group.

Among the above groups, an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a cycloalkylene group, and a silicon-containing group are particularly preferable. Further, it is preferred that ^{Q 1} and ^{Q 2} are the same.

R ^{1 to} R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms (G2), halogen-containing groups (H2), silicon-containing groups (Si2), oxygen-containing groups (O2), and nitrogen-containing groups (N2). ) Or a sulfur-containing hydrocarbon group (S2), which may be the same or different from each other.

The hydrocarbon group (G2) having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups), and an aromatic hydrocarbon having 6 to 40 carbon atoms. It is a group (aryl group). The hydrocarbon group having 1 to 20 carbon atoms is more preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The range of hydrocarbon groups having 1 to 20 carbon atoms also includes substituents having an aromatic structure such as an arylalkyl group (arylalkyl group).

The hydrocarbon group (G2) having 1 to 40 carbon atoms is not particularly limited as long as the effects of the present invention are exhibited, and for example, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group. Group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl, iso-propyl group, sec-butyl ( Butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl ( 3-Methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, sheamil (1,2-dimethylpropyl) group, pentan-3-yl group, 2- Methylpentyl group, 3-methylpentyl group, iso-hexyl (4-methylpentyl) group, 1,1-dimethylbutyl (2-methylpentane-2-yl) group, 3-methylpentane-2-yl group, 4 -Methylpentane-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 3- Methylpentane-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentane-3-yl group, heptan-4-yl group, 2,4-dimethylpentane -3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3- A linear or branched alkyl group having 1 to 20 carbon atoms, such as a trimethylbutan-2-yl group, a 2,3,4-trimethylpentane-3-yl group;

Vinyl group, allyl group, propenyl (propa-1-en-1-yl ) group , iso- propenyl (propa-1-en-2-yl ) group , allenyl (propa-1,2-dien-1-yl ) Group, porcine-3-en-1-yl group, crotyl (but-2-en-1-yl) group, porcine-3-en-2-yl group, metalryl (2-methylallyl) group, erythrenyl (buta-) 1,3-Dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3-methylbutan-3) -En-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methyl-but-2-en-1-yl) group , 2-Methyl-but-2-ene-1-yl group, penta-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-en-3-yl group Il group, penta-2,4-diene-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl (2-methyl-) Buta-1,3-dien-1-yl) group, penta-2,4-dien-2-yl group, hexa-5-ene-1-yl group, hexa-4-en-1-yl group, hexa -3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-ene-1-yl group, 3-methyl-penta-4-ene-1-yl group , 2-Methyl-penta-4-ene-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-ene-1-yl group, 3-methyl-penta-3-3 En-1-yl group, 2,3-dimethyl-but-2-ene-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3-yl group, Hexa-3,5-diene-1-yl group, hexa-2,4-diene-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-buta-1 , 3-Diene-1-yl group, hexa-1,3,5-triene-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group A linear or branched alkenyl group or unsaturated double bond-containing group having 2 to 40 carbon atoms such as;

Ethynyl group, propa-2-in-1-yl group, propargyl (propa-1-in-1-yl) group, pig-1-in-1-yl group, bututa-2-in-1-yl group, Buta-3-in-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in- 1-yl group, 3-methyl-buta-1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4- In-2-yl group, hexa-1-in-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, 2-methyl-penta-3-in-2-yl group, Straight chain having 2 to 40 carbon atoms such as 2,2-dimethyl-but-3-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group Deformal or branched alkynyl group or unsaturated triple bond containing group;

Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, Kuminyl (4-iso-propylbenzyl) group, 2,4,6- Tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group, Kumil (2-phenylpropan-2-) Il) group, 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2- Il group, 2- (3,5-di-tert-butylphenyl) propan-2-yl group, 3-phenylpentane-3-yl group, 4-phenylhepta-1,6-dien-4-yl group, 1,2,3-Triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-3-ene-1-yl group, 1,1, 1,2-Triphenylethyl group, trityl (triphenylmethyl) group, tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl (2-phenylvinyl) group, 2- (2-methylphenyl) ) Ethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4, 6-Tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, 2-methyl-1-phenylpropane -2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neofil (2-methyl-2-phenylpropyl) group, 3-methyl-3-phenylbutyl group, 2-methyl- 4-Phenylbutane-2-yl group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group , 2- (Tetrahydro-1-indacenyl) propan-2-yl group, (Tetrahydro-1-indacenyl) diphenylmethyl group, 2- (Tetrahydro-1-indacenyl) ethyl group, 2- (1-benzoindenyl) propane -2-yl group, (1-benzoindenyl) diphenylmethyl group, 2- (1-benzoindeni) Le) Ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azulenyl) propan-2-yl An aromatic-containing linear or branched alkyl group having 7 to 40 carbon atoms and an unsaturated double bond-containing group such as a group, a (1-azulenyl) diphenylmethyl group, and a 2- (1-azulenyl) ethyl group. ;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, Cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2- Methylbicyclo [2.2.1] heptane-2-yl group, 7-methylbicyclo [2.2.1] heptane-7-yl group, bicyclo [2.2.2] octane-1-yl group, bicyclo [2.2.2] Octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl) , 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indasenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group, etc. have 3 to 40 carbon atoms. Cyclic saturated and unsaturated hydrocarbon groups;

Phenyl group, trill (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, juryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group , Allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, metallicylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3, 5-Di-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrosenyl group, etc., aromatic substitutions with 6 to 40 carbon atoms ( Aryl) group; and the like.

Among the linear or branched alkyl groups having 1 to 20 carbon atoms, particularly methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-Heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butane-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) ) Group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, pentan-3-yl group, iso-hexyl (4-) Methylpentyl) group, 1,1-dimethylbutyl (2-methylpentane-2-yl) group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 3-methylpentane -3-yl group, heptan-4-yl group, 2,4-dimethylpentane-3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4- Il group, 4-propylheptan-4-yl group and the like can be mentioned, and more preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group and iso. -Propyl group and tert-butyl (2-methylpropan-2-yl) group are preferable.

Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, buta-3-ene-1-yl group and crotyl are particularly present. (Buta-2-en-1-yl) group, metalryl (2-methylallyl) group, penta-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, Penta-1,4-diene-3-yl group, hexa-5-ene-1-yl group, 2-methylpenta-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl Examples thereof include a group, a 2- (cyclopentadienyl) ethyl group and the like, and more preferably, a vinyl group, an allyl group, a buta-3-ene-1-yl group, a penta-4-ene-1-yl group and the like. , Plenyl (3-methyl-but-2-ene-1-yl) group, hexa-5-ene-1-yl group are preferable.

Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, propa-2-in-1-yl group, propargyl (propa-1) in particular. −In-1-yl) group, porcine-2-in-1-yl group, porcine-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl Il group, 3-methyl-buta-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5- Examples thereof include an in-1-yl group, and more preferably, a propa-2-in-1-yl group, a propargyl (propa-1-in-1-yl) group, a buta-2-in-1-yl group and the like. An yl group and a porcine-3-in-1-yl group are preferable.

Among the aromatic-containing linear or branched alkyl groups having 7 to 40 carbon atoms and unsaturated double bond-containing groups, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, among others, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group 3,5-Di-tert-butylbenzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2 -Phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- (2,4) , 6-Tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, styryl (2-phenylvinyl) Group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neofil (2-methyl-2-phenylpropyl) group, cyclopentadienyl Diphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group , (9-Fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group and the like, more preferably benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) and the like. ) Group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group are preferable.

Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, in particular, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, 1 -Allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1 -Methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [ 2.2.1] heptane-2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like. Of these, a cyclopentyl group, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group and a 1-adamantyl group are more preferable.

Among the aromatic substituted (aryl) groups having 6 to 40 carbon atoms, phenyl group, tolyl (methylphenyl) group, xsilyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) Group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di -Tart-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrosenyl group and the like. More preferably, a phenyl group, a trill (methylphenyl) group, a xsilyl (dimethylphenyl) group, a mesityl (2,4,6-trimethylphenyl) group, a cumenyl (iso-propylphenyl) group, 2,6-di-iso -Propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl A group, a biphenyl group, a phenanthryl group, and an anthrasenyl group are preferable.

The halogen-containing group (H2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Ethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group , Chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, tri Fluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert- Butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group , Difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoro Examples thereof include a methylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, and a trifluoromethylthio group.

Among the halogen-containing groups (H2), in particular, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, 4, 4,4-Trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, Pentafluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, trifluoromethylthio group , Etc., and more preferably, trifluoromethyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, pentafluorobiphenyl group, trifluoromethoxy group, pentafluoro. A phenoxy group is preferred.

The silicon-containing group (Si2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, and a tert-butyldimethylsilyl group. , Tert-Butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, di-n-butyl (indenyl) silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4- Trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris (trimethylsilyl) silylphenyl group, etc. Can be mentioned.

Among the silicon-containing groups (Si2), trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadi Enyldiphenylsilyl group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso- Examples thereof include a propylsilylphenyl group and a 4-triphenylsilylphenyl group, more preferably a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group and a 4-triethylsilylphenyl group. A 4-tri-iso-propylsilylphenyl group is preferred.

The oxygen-containing group (O2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, sec- Butoxy group, iso-butoxy group, tert-butoxy group, metalryloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy Group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxy Ethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxy Vinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydrofuryl group, pyranyl group , Tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group and the like.

Among the oxygen-containing groups (O2), particularly, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, Truyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, Methoxyaryl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group , Phenoxyphenyl group, methylenedioxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methylfuryl group, tetrahydropyranyl group, flofuryl group, benzofuryl group, dibenzofuryl group, etc. Among them, more preferably, methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group. , Phenoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, frill group, methyl frill group, benzofuryl group, dibenzofuryl group are preferable.

The nitrogen-containing group (N2) is not particularly limited as long as the effect of the present invention is exhibited, and for example, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, or a dibenzyl. Amino group, pyrrolidinyl group, piperidinyl group, molyphoryl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinyl Ethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinyl vinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group , Aminophenyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl Group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrrolyl group, phenylpyrrolill group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, Examples thereof include indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group and benzoxazolyl group.

Among the nitrogen-containing groups (N2), in particular, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group and benzylamino. Methyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group , Pyrrolidinyl phenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl Group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidini Examples thereof include a ru group, a benzoimidazolyl group, an oxazolyl group, an oxazolidinyl group and a benzoxazolyl group, and more preferably, an amino group, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a dimethylaminophenyl group and a pyrrolyl group. Dinylphenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, durolidinyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group are preferable.

The sulfur-containing group (S2) is not particularly limited as long as the effects of the present invention are exhibited, and for example, a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, and a phenylthio. Methyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, Benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, phenylthioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group , Benzothienyl phenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofryl group, thienotienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl Examples thereof include a group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, a thiazolidinyl group and the like.

Among the sulfur-containing groups (S2), a thienyl group, a methylthienyl group, a thienofryl group, a thienotienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group and a benzothiazolyl group are particularly preferable. ..

Of R ^{1 to} R ⁶ , adjacent substituents may be bonded to each other to form a ring, and when a plurality of rings are present, they may be the same or different from each other.

Of R ^{1 to} R ⁶ , when adjacent substituents are bonded to each other to form a ring, a saturated or unsaturated hydrocarbon group having a 5- to 8-membered ring fused to the cyclopentadienyl ring portion and a saturated or unsaturated hydrocarbon group. A heterocycle may be formed. The ring is not particularly limited as long as the effect of the present invention is exhibited, but is preferably a 5- or 6-membered ring. As a structure combined with the cyclopentadienyl moiety of the mother nucleus, for example, a substituted cyclopentapyrrole ring, a substituted cyclopentaindole ring, a substituted cyclopentathiophene ring, a substituted cyclopentabenzothiophene ring, a substituted indene ring, a substituted benzoinden ring, Examples thereof include a substituted tetrahydroindene ring, a substituted azulene ring, a substituted dihydroazulene ring, a substituted tetrahydroazulene ring, and a substituted hexahydroazulene ring. A substituted indene ring and a substituted tetrahydroindene ring are preferable.

R ¹ and Q ¹ , R ⁶ and Q ¹ , R ³ and Q ² , R ⁴ and Q ² may be combined with each other to form a ring, and if there are multiple rings, they may be the same or different from each other. May be good. The ring is not particularly limited as long as the effect of the present invention, it is preferably a saturated 5-membered ring or bicyclic saturated 5-membered ring containing Q ¹ or Q ^2. Examples of the structure in this case include a cyclopentane ring matrix, an octahydroindene ring matrix, and an octahydropentane ring matrix.

R ^{1 to} R ⁶ are particularly preferably hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups or nitrogen-containing groups, and have hydrogen atoms or carbon atoms 1 to 20. It is more preferably a hydrocarbon group.

At least one of R ^{1 to} R ⁶ is a substituent represented by the general formula [2] or a substituent represented by the general formula [3]. In the general formulas [2] and [3], m is an integer of 1 to 8, preferably 1 to 4, and more preferably 1 to 2. The “wavy line” portion in the general formulas [2] and [3] means a cyclopentadienyl structural portion to which this substituent is bonded. In the present invention, the amount of long-chain branched (LCB) introduced is significantly reduced by using the novel transition metal compound of the present invention in which at least one of R ^{1 to} R ⁶ has such a specific substituent. It is possible to provide a catalyst for olefin polymerization which can improve the polymerization activity without any problem. For example, as compared with a catalyst for olefin polymerization using a transition metal compound having only a substituent such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, olefin polymerization using a novel transition metal compound of the present invention The catalyst used is particularly excellent in olefin polymerization activity.

Further, the transition metal compound [A] is preferably a transition metal compound represented by the general formula [4].

In the general formula [4], M, X, n and ^R 1 to R ⁶ are the same M, X, and n and ^R 1 to R ⁶ in the general formula [1].

Q ³ and Q ⁴ are carbon atom or a silicon atom may be the same or different from each other. In particular, they are preferably the same.

R ^{7 to} R ¹⁰ are hydrogen atoms, hydrocarbon groups having 1 to 40 carbon atoms (G3), halogen-containing groups (H3), silicon-containing groups (Si3), oxygen-containing groups (O3), and nitrogen-containing groups (N3). ) Or a sulfur-containing group (S3), which may be the same or different from each other.

Specific examples of hydrocarbon groups (G3), halogen-containing groups (H3), silicon-containing groups (Si3), oxygen-containing groups (O3), nitrogen-containing groups (N3) and sulfur-containing groups (S3) having 1 to 40 carbon atoms. Examples and preferred specific examples are the same as the specific examples and preferred specific examples mentioned in R ^{1 to} R ⁶ above.

R ⁷ and R ⁸ and R ⁹ and R ¹⁰ may be combined with each other to form a ring, and when a plurality of rings are present, they may be the same or different from each other. Specific examples and preferable specific examples of the ring containing Q ³ or Q ⁴ are the same as those of the cycloalkylene group and the cyclomethylene silylene group in the specific examples and preferable specific examples mentioned in Q ¹ and Q ² . In particular, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclodimethylenesilylene, cyclotrimethylenecilylene, cyclotetramethylenesilylene, and cyclopentamethylenesilylene are preferable.

R ⁷ and R ¹ , R ⁸ and R ⁶ , R ⁹ and R ³ , R ¹⁰ and R ⁴ may be combined with each other to form a ring, which may be the same or different if there are multiple rings. You may. The ring is not particularly limited as long as the effect of the present invention, it is preferably a saturated 5-membered ring or bicyclic saturated 5-membered ring containing Q ³ or Q ^4. Examples of the structure in this case include a cyclopentane ring matrix, an octahydroindene ring matrix, and an octahydropentane ring matrix.

R ^{7 to} R ¹⁰ are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group or a nitrogen-containing group, and a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms. More preferably it is a group.

Further, it is preferable that R ⁷ and R ⁸ are the same group, R ⁹ and R ¹⁰ are the same group, and R ^7- Q ^3- R ⁸ and R ^9- Q ^4- R ¹⁰ are the same group. Is more preferable.

[Method for producing transition metal compound [A]]
An example of the method for producing the transition metal compound [A] of the present invention is shown below. However, the present invention is not limited to those produced by the following methods.

First, the starting material, the compound in which the substituted cyclopentadiene compound is crosslinked, can be produced using the substituted cyclopentadiene compound as a raw material. Examples of the manufacturing method thereof include "Organometallics 1991, 10, 3739.", International Publication No. 2004/066689 by the Applicant, JP-A-2009-143901, and JP-A-2002-308893 by the Applicant. Examples thereof include the methods described in International Publication No. 2012/07789, International Publication No. 2013/031779, and the like.

The precursor compound (ligand) of the transition metal compound [A] in which the substituted cyclopentadiene compound is doubly crosslinked at the adjacent position can be produced by using the compound in which the substituted cyclopentadiene compound is crosslinked as a raw material. As the production method thereof, for example, in addition to the method for producing a compound in which the substituted cyclopentadiene compound is crosslinked, "Organometallics 1991, 10, 1787.", International Publication No. 1995/009172, JP-A-11. The method described in Japanese Patent Application Laid-Open No. -322774 can be mentioned.

The target transition metal compound [A] can be produced by using the precursor compound (ligand). Examples of the production method include those listed as the method for producing the precursor compound (ligand), "Organometallics 1993, 12, 1931.", "Organometallics 2001, 20, 3035.", US Pat. No. 5972822, JP-A-10-109996, "J. Organometallic Chem. 1997, 527, 297.", JP-A-2002-88092, "Organometallics 2012, 31, 4340.", International Publication by the Applicant. The method described in No. 2004/029062 and the like can be mentioned.

The transition metal compound [A] and its precursor compound (ligand) have two directions (front surface and back surface) of a cyclopentadienyl ring portion that bonds with the central metal across the crosslinked portion. Therefore, if there is no intramolecular symmetric mirror image plane on one cyclopentadienyl ring and the two cyclopentadienyl ring portions bonded to the central metal with the crosslinked portion in between are the same racemate. There are two types of structural isomers, and meso, and when the two cyclopentadienyl ring portions are different from each other, there are two types of structural isomers, pseudo-racemic and pseudo-meso.

Further, the substituents represented by Q ¹ and Q ² in the general formula [1], R ⁷ −Q ^{3 −} R ⁸ in the general formula [4], and R ⁹ −Q ⁴ −R ¹⁰ are shown. Structural isomers also exist when the two crosslinked moieties represented by the substituents are different, or when the substituents represented by R ^{7 to} R ¹⁰ in the general formula [4] are not the same.

Purification of these structural isomer mixtures, fractionation of racemic and pseudo-racemic forms, or selective production of racemic and pseudo-racemic forms is also possible. Examples of the production method include the methods described in those listed as the production methods for the transition metal compound [A].

Specific examples of the transition metal compound [A] obtained by the above-mentioned production method and the like are shown below, but the scope of the present invention is not particularly limited by this. In the present invention, the transition metal compound [A] may be used alone, in combination of two or more, racemic and pseudo-racemic, and a mixture of structural isomers. It may be used in combination of these above.

For convenience, the ligand structure of the transition metal compound [A] of the present invention excluding MX _n (metal moiety) is a cyclopentadienyl ring moiety, a cyclopentadienyl ring partial substituent (Z), and a cyclopentadienyl ring moiety. It is divided into six parts: a substituent (Y), a cyclopentadienyl ring partial substituent (W), a cyclopentadienyl ring partial substituent (V), and a crosslinked moiety structure.

Cyclopentadienyl ring moiety abbreviation α, cyclopentadienyl ring partial substituent (Z) abbreviation β, cyclopentadienyl ring partial substituent (Y) abbreviation γ, cyclopentadienyl ring partial substitution The abbreviation of the group (W) is δ, the abbreviation of the cyclopentadienyl ring partial substituents (V ¹ and V ² ) is ε, the abbreviation of the structure of the crosslinked moiety is ζ, and the abbreviations of each substituent are shown in Tables 1 to 6. Shown in.

In Table 1, Cp in the figure of α-10, α-11 and α-12 indicates that the other cyclopentadienyl ring is bound, and is shown in Table 6 at the position adjacent to the binding site. It represents that it is bound by the cross-linking site.

Specific examples of the metal portion MX _{n is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2 , Ti (η ⁴ -1,3- butadienyl), Ti (η ⁴ -1,3- pentadienyl), Ti (η ⁴ -2,4- hexadienyl), Ti (η ⁴ -1,4- diphenyl-1, _{3-pentadienyl), Ti (CH 2 -Si (} Me) 3) 2, Ti (OMe) 2, Ti (OiPr) 2, Ti (NMe 2) 2, Ti (OMs) 2, Ti (OTs) 2, Ti _{(OTf) 2, ZrF 2,} ZrCl 2, ZrBr 2, ZrI 2, Zr (Me) 2, Zr (Bn) 2, Zr (Allyl) 2, Zr (CH 2 -tBu) 2, Zr (η 4 -1 , 3-butadienyl), Zr (eta ⁴ -1,3-pentadienyl), Zr (η ⁴ -2,4- hexadienyl), Zr (η ⁴ -1,4- diphenyl-1,3-pentadienyl), Zr ( CH _2- Si (Me) ₃ ) ₂ , Zr (OMe) ₂ , Zr (OiPr) ₂ , Zr (NMe ₂ ) ₂ , Zr (OMs) ₂ , Zr (OTs) ₂ , Zr (OTf) ₂ , HfF _{2 , HfCl 2, HfBr 2, HfI} 2, Hf (Me) 2, Hf (Bn) 2, Hf (Allyl) 2, Hf (CH 2 -tBu) 2, Hf (η 4 -1,3- butadienyl), Hf (eta ⁴ -1,3-pentadienyl), Hf (η ⁴ -2,4- hexadienyl), Hf (η ⁴ -1,4- _{diphenyl-1,3-pentadienyl), Hf (CH 2 -Si (} Me) ₃ ) ₂ , Hf (OMe) ₂ , Hf (OiPr) ₂ , Hf (NMe ₂ ) ₂ , Hf (OMs) ₂ , Hf (OTs) ₂ , Hf (OTf) _{2, and the} like. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and OMs is a methanesulfonate. The group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

For example, the cyclopentadienyl ring portion is α-4 in Table 1, the cyclopentadienyl ring partial substituent (Z) is β-10 in Table 2, and the cyclopentadienyl ring partial substituent (W) is shown in Table 2. Δ-1 in 4, cyclopentadienyl ring partial substituent (V ¹ ) is ε-2 in Table 5, cyclopentadienyl ring partial substituent (V ² ) is ε-2 in Table 5, cross-linking When the portion is composed of the combination of ζ-27 in Table 6 and the MX _{n of} the metal portion is ZrMe ₂ , the compound is represented by the following formula [5].

For example, if the two substituted cyclopentadienyl ring moieties bonded to the metal moiety MX _n and the crosslinked structure are not the same but different, one cyclopentadienyl ring moiety is α-2 in Table 1. , Cyclopentadienyl ring partial substituent (Z) is β-1 in Table 2, cyclopentadienyl ring partial substituent (Y ³ ) is γ-1, cyclopentadienyl ring partial substituent (Y3) in Table 3. (Y ⁴ ) is γ-9 in Table 3, the other cyclopentadienyl ring moiety is α-2 in Table 1, and the cyclopentadienyl ring partial substituent (Z) is β in Table 2. -3, Cyclopentadienyl ring partial substituent (Y ³ ) is γ-5 in Table 3, cyclopentadienyl ring partial substituent (Y ⁴ ) is γ-1 in Table 3, one crosslinked moiety is When ζ-31 in Table 6 and one of the crosslinked portions are composed of a combination of ζ-2 in Table 6 and the MX _{n of} the metal portion is Hf (NMe ₂ ) ₂ , the following formula [6] is used. It becomes the represented compound.

For example, one cyclopentadienyl ring moiety is α-10 in Table 1, the cyclopentadienyl ring partial substituent (Z) is β-5 in Table 2, and the other cyclopentadienyl ring moiety is. Is α-8 in Table 1, cyclopentadienyl ring partial substituent (Z) is β-1 in Table 2, cyclopentadienyl ring partial substituent (W) is δ-30 in Table 4, and cross-linking. portion is a combination of zeta-21 in Table 6, when MX _n of the metal portion is Ti (η ⁴ -1,3- pentadienyl) is a compound represented by the following formula [7].

The reason why the transition metal compound of the present invention exhibits a unique performance (for example, excellent polymerization activity) is not always clear, but the performance is the general formula [2] or [3] introduced on the cyclopentadienyl ring. ], That is, it is considered to be caused by the substituents of β-2 to β-17 in Table 2.

<Catalyst for olefin polymerization>
The catalyst for olefin polymerization of the present invention is a catalyst characterized by containing a novel transition metal compound [A] represented by the above general formula [1], preferably the general formula [4] described above. In addition, in this specification, an olefin refers to any compound having a polymerizable double bond.

The catalyst for olefin polymerization of the present invention further reacts with the organometallic compound (B-1), the organoaluminum oxy compound (B-2), and the transition metal compound [A] to form an ion pair (B). It is preferable to contain at least one compound (B) selected from the group consisting of -3). Hereinafter, each component contained in the catalyst for olefin polymerization will be described as needed.

(Organometallic compound (B-1))
As the organometallic compound (B-1), specifically, at least one of the groups 1, 2, 12, and 13 of the periodic table represented by the following general formulas (B-1a) to (B-1c). Examples include compounds containing atoms.

R ^a _p Al (OR ^b ) _q H _r Y _s ... (B-1a)
(In the general formula (B-1a), ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen atom. , P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is the number of 0 ≦ s <3, and p + q + r + s = 3). Organic aluminum compound

M ³ AlR ^c1 ₄ ... (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c1 represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkylated product of alkali metal and aluminum of Group 1 of the Ritsuryo

R ^d R ^e M ⁴ ... (B-1c)
(In the general formula (B-1c), R ^d and ^Re may be the same as or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg. , Zn or Cd.) A dialkyl compound with an alkaline earth metal of Group 2 or a metal of Group 12 of the periodic table.

Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.

R ^a _p Al (OR ^b ) _3-p ... (B-1a-1)
(In the formula (B-1a-1), ^Ra and R ^b may be the same as or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferable. Is a number of 1.5 ≤ p ≤ 3).

R ^a _p AlY _3-p ... (B-1a-2)
(In the formula (B-1a-2), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably 0 <p <3. The organic aluminum compound represented by).

R ^a _p AlH _3-p ... (B-1a-3)
(In the formula (B-1a-3), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p <3). Represented organic aluminum compound

R ^a _p Al (OR ^b ) _q Y _s ... (B-1a-4)
(In the formula (B-1a-4), ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen. An organic aluminum compound representing an atom, where p is 0 <p ≦ 3, q is 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as the organic aluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri-n-alkylaluminum such as;

Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Tri-branched alkylaluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;

Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;

Triarylaluminum such as triphenylaluminum and tritrylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (In the formula, x, y, z are positive numbers and z ≧ 2x), etc. Triisoprenyl aluminum Trialkenyl aluminum such as;

Alkoxides such as isobutylaluminum methoxydo, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxydo and butyl aluminum sesquibutoxide;

Partially alkoxylated alkylaluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _0.5 (in the formula, ^Ra and R ^b may be the same or different from each other. Shows hydrocarbon groups with 1 to 15 carbon atoms, preferably 1 to 4);

Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;

Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;

Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;

Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;

Other partially hydrogenated alkylaluminum such as ethylaluminum dihydride, alkylaluminum dihydride such as propylaluminum dihydride;

Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid; and the like.

A compound similar to (B-1a) can also be used in the present invention, and examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. More specifically, (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like can be mentioned.

Examples of the compound represented by the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the compound represented by the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, and di-. Examples thereof include n-butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, and diethyl cadmium.

Other organic metal compounds (B-1) include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, and propylmagnesium chloride. , Butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

Further, a compound such that the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, etc. Can also be used as.

Among the organometallic compounds (B-1), organoaluminum compounds are preferable from the viewpoint of catalytic activity.

The organometallic compound (B-1) is used alone or in combination of two or more.

(Organoaluminium oxy compound (B-2))
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or is a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. You may.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.

(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered solution of aluminoxane by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing alminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

Organoaluminium compounds are used alone or in combination of two or more.

Examples of the solvent used for the preparation of alminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum distillates such as gasoline, kerosene, light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially chlorine Examples thereof include hydrocarbon solvents such as isomers and bromines. Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable. These solvents can be used alone or in combination.

The organoaluminum oxy compound (B-2) includes an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b) and a repeating unit represented by the following general formula (B-2c). Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit represented by the following general formula (B-2d) as a structure.

In the general formulas (B-2a), (B-2b) and (B-2c), ^Re is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and is specific. Methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group. , Tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, ethylphenyl group and other hydrocarbon groups can be exemplified. Of these, a methyl group, an ethyl group and an isobutyl group are preferable, and a methyl group is particularly preferable. Some of the R ^e is chlorine, substituted with a halogen atom such as bromine, and halogen content may be 40 wt% or less. In the general formulas (B-2c) and (B-2d), a straight line in which one is not connected to an atom indicates a bond with another atom (not shown).

In the general formulas (B-2a) and (B-2b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, particularly preferably 10 to 100.

In the general formulas (B-2c) and (B-2d), s and t represent integers of 1 or more, respectively.

Aluminoxane having a repeating unit represented by the general formula (B-2c) and a repeating unit represented by the general formula (B-2d) has a molecular weight within the range of 200 to 2000 measured by the freezing point depression method of benzene. It is preferable to have.

The benzene-insoluble organoaluminum oxy compound has an Al component that dissolves in benzene at 60 ° C., which is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is, with respect to benzene. It is preferably insoluble or sparingly soluble.

As the organoaluminum oxy compound (B-2), for example, an organoaluminum oxy compound containing boron represented by the following general formula (B-2e) can be mentioned.

(In the general formula (B-2e), R ^f represents a hydrocarbon group having 1 to 10 carbon atoms, and 4 R ^g each independently have a hydrogen atom, a halogen atom or a carbon atom number of 1 to 10. Indicates the hydrocarbon group of.)

The organoaluminum oxy compound containing boron represented by the general formula (B-2e) contains, for example, an alkylboronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. It can be produced by reacting under an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

R ^f −B (OH) ₂ ... (B-2f)
(In the general formula (B-2f), R ^f represents the same group as R ^f in the general formula (B-2e).)

Specific examples of the alkylboronic acid represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-hexyl. Examples thereof include boronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These are used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

When an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination with the transition metal compound [A], it exhibits extremely high polymerization activity with respect to the olefin compound.

The organoaluminum oxy compound (B-2) is used alone or in combination of two or more.

(Compound (B-3) that reacts with the transition metal compound [A] to form an ion pair)
Examples of the compound (B-3) (hereinafter, referred to as “ionized ionic compound”) that reacts with the transition metal compound [A] to form an ion pair include JP-A-1-501950 and JP-A-1-501. Lewis acids and ions described in JP-A-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321106, and the like. Examples thereof include sex compounds, borane compounds and carborane compounds. In addition, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group) is used. For example, trifluoroborone, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, etc. Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (B-3a).

(In the general formula (B-3a), R ^h is a ferrosenium cation having H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptiltyrienyl cation or a transition metal, and R ⁱ ~ R ^l may be the same or different from each other and may be an organic group, preferably an aryl group or a substituted aryl group).

Specific examples of the carbocation cation include trisubstituted carbocation cations such as triphenyl carbocation cation, tri (methylphenyl) carbocation cation, and tri (dimethylphenyl) carbocation cation.

Specific examples of the ammonium cation include lower alkyl such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation and di (n-octadecyl) methylammonium cation. Higher alkyl trialkylammonary ammonium cations; N, N-dialkylaniliniums such as N, N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations Cities: Dialkylammonium cations such as di (isopropyl) ammonium cations and dicyclohexylammonium cations can be mentioned.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ^h , a carbonium cation and an ammonium cation are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Further, as the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-). Trill) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium Tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (N-Butyl) Ammonium Tetra (o-Trill) Boron, Di (Octadecyl) Methylammonium Tetraphenyl Boron, Di (Octadecyl) Methylammonium Tetrakiss (p-Trill) Boron, Di (Octadecyl) Methylammonium Tetrakiss (o-Trill) Boron, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) boron, di (octadecyl) methylammonium tetrakis (2,4-dimethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5-dimethylphenyl) boron, Di (octadecyl) methylammonium tetrakis (4-trifluoromethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5-ditrifluoromethylphenyl) boron and other di (octadecyl) methylammonium, which are lower to higher alkyl An alkylammonium salt having the above can be exemplified.

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4. , 6-Pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula (B-3b) or (B-3c) and the like can also be mentioned.

（式（Ｂ−３ｂ）中、Ｅｔはエチル基を示す。）

(In formula (B-3b), Et represents an ethyl group.)

(In formula (B-3c), Et represents an ethyl group.)

As a borane compound which is an example of an ionized ionic compound (compound (B-3)), specifically, for example, decaborane;

Bis [tri (n-butyl) ammonium] nonabolate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anion salts such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;

Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Salt; etc.

Specific examples of the carborane compound, which is an example of an ionized ionic compound, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecabolan, and dodecahydride-1-phenyl-1,3. -Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecabolan, 2,7-Dicarbaundecabolan, Undecahydride-7,8-dimethyl-7,8-dicarbaundecabolan, Dodecahydride-11-methyl-2,7-dicarbundecabolan, tri (n-butyl) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecabolate , Tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecabolate , tri (n-butyl) ammonium 7-carbundecaborate, tri (n-butyl) ammonium 7 , 8-dicarbundecaborate, tri (n-butyl) ammonium 2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbundecaborate, tri (n) -Butyl) ammonium undecahydride-8-ethyl-7,9-dicarbundecabolate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ) Ammonium undecahydride-8-allyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbundecaborate, tri (n-butyl) ammonium Undeca Hydlide-4,6-dibromo-7-carb Undecaborate and other anion salts;

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Telate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydride-7,8-Dicarba Undecaborate) Cobalate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydlide-7) , 8-dicarbundecaborate) Niklate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-dicarbundecaborate) Copper Acidate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Hydrochloride (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarba Undecaborate) Tetrate (III), Tri (n-Butyl) Ammonium Bis (Nonahydrate-7,8-Dimethyl-7,8-Dicarbundecaborate) Chromate (III), Tri (n-Butyl) Ammonium Bis (N-butyl) Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydrate-7-carbaundecaborate) chromate (III) , Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Manganate (IV), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydlide-7-Cal) Bound decaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV) and other metal carborane anion salts; etc. Can be mentioned.

Heteropoly compounds, which are examples of ionized ionic compounds, include atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. It is a compound. Specifically, limbanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, tungstic acid, germanomolybdic acid, arsenic molybdic acid, tungstic acid, phosphorus. Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdate vanadic acid, phosphombdate vanadic acid, germanotangstvanadic acid, phosphomolybdate tongue tungstic acid, germanomolybdate tongue tungstic acid, phosphomolybdate tungstic acid , Phospholybdoniobic acid, and salts of these acids, but not limited to. Further, the salt includes the acid, for example, an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium. , Salts with cesium, barium and the like, and organic salts such as triphenylethyl salt and the like.

An isopoly compound, which is an example of an ionized ionic compound, is a compound composed of a metal ion of one atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ion species of a metal oxide. Can be done. Specific examples include, but are not limited to, vanadate, niobate, molybdic acid, tungstic acid, and salts of these acids. Examples of the salt include metals of Group 1 or Group 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Salts, organic salts such as triphenylethyl salt and the like.

The ionized ionic compound (compound (B-3) that reacts with the transition metal compound [A] to form an ion pair) is used alone or in combination of two or more.

The polymerization catalyst of the present invention comprises the above-mentioned transition metal compound [A], preferably an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and an ionized ionic compound (B-3). The following carrier [C] may be contained, if necessary, together with at least one compound [B] selected from the group.

[[C] Carrier]
The carrier [C] is an inorganic or organic compound and is a solid in the form of granules or fine particles. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer having good morphology can be obtained.

As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2, and the} like, or a composite or mixture containing these. Can be used. Further, for example, natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TIO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TIO _2- MgO Etc. can also be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

The properties of such porous oxides differ depending on the type and manufacturing method, but preferably used porous oxides have a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. It is desirable that the pore volume is in the range of ² / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d).

Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane does not contain inorganic solid components such as silica and alumina and organic polymer components such as polyethylene and polystyrene, and is solidified with an alkylaluminum compound as a main component. Is shown. The meaning of "solid state" used in the present invention is to maintain a substantially solid state in a reaction environment in which the aluminoxane component (B-2) is used. More specifically, for example, when the component [A] and the component [B] are brought into contact with each other to prepare a solid catalyst component for olefin polymerization as described later, an inert hydrocarbon solvent such as hexane or toluene used in the reaction is used. Medium, it indicates that the component [B] is in a solid state under a specific temperature / pressure environment. Further, for example, when suspension polymerization is carried out using a solid catalyst component for olefin polymerization prepared by using the component [B] as described later, a specific temperature and pressure are used in a hydrocarbon solvent such as hexane, heptane, and toluene. It is also a necessary requirement that the component [B] contained in the catalyst component in the environment is in a solid state. The same applies to bulk polymerization in which polymerization is carried out in a liquefied monomer instead of a solvent, and vapor phase polymerization in which polymerization is carried out in a monomer gas.

Whether or not the component [B] is in a solid state under the above environment is the easiest method to visually confirm, but it is often difficult to visually confirm, for example, during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after the polymerization and the state of adhesion to the reactor. On the contrary, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the component [B] is eluted in the polymerization environment, the gist of the present invention is not deviated. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of abundance of the amorphous polymer, but the polymer bulk density is preferable from the viewpoint of quantitativeness. The bulk density in the present invention is usually 0.01 to 0.9, preferably in the range of 0.05 to 0.6, and more preferably in the range of 0.1 to 0.5.

The solid aluminoxane dissolves in n-hexane maintained at a temperature of 25 ° C. in a range of usually 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%. To do.

The dissolution ratio of solid aluminoxane to n-hexane was determined by adding 2 g of a solid aluminoxane carrier to 50 ml of n-hexane maintained at 25 ° C., stirring for 2 hours, and then using a G-4 glass filter. The solution part was separated and determined by measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane, known solid aluminoxane can be used endlessly. As known manufacturing methods, for example, JP-A-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. Examples thereof include Japanese Patent Application Laid-Open No. -38410, Japanese Patent Application Laid-Open No. 2000-95810, and International Publication No. 2010/55652.

The average particle size of the solid aluminoxane is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm.

The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. For the particle size of solid aluminoxane, the maximum length of the Pythagorean method was measured from a particle image. That is, the length of the particle image sandwiched between two parallel lines is measured in each of the horizontal and vertical directions, and the calculation is performed using the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5

The weight average particle size of the solid aluminoxane is calculated by the following formula using the particle size obtained above.
Average particle size = Σnd ⁴ / Σnd ³ (where n; number of particles, d; particle size)

The solid aluminoxane preferably has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. It is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it into fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Furthermore, clays, as clay minerals or ion-exchangeable layered compound, hexagonal close packing type, antimony type, CdCl ₂ type, and the like can be exemplified ionic crystalline compounds having a layered crystal structure, such as a CdI ₂ type.

Furthermore, as clays and clay minerals, kaolin, bentonite, wood knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, dicite, etc. Halloy site etc. can be mentioned.

The ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples thereof include crystalline acid salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ and H ₂ O.

Such clays, clay minerals, or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, and 0.3 to 5 cc / g, as measured by a mercury intrusion method and having a radius of 20 Å or more. Is particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter. When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.

It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ , ZrCl _4, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+, and other metal hydroxide ions. Can be mentioned. These compounds are used alone or in combination of two or more. Further, when these compounds are intercalated, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO ₂ and the like can coexist. Further, examples of the pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Of these, preferred are clays or clay minerals, with particularly preferred being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

As described above, the carrier [C] is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a polymer produced mainly of α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. The polymers produced as, and their variants can be exemplified.

The catalyst for olefin polymerization of the present invention includes the transition metal compound [A], preferably the compound [B], and if necessary, a carrier [C], and if necessary, the following specific organic compound component [D]. Can also be included.

[[D] Organic compound component]
The organic compound component [D] is used for the purpose of improving the polymerization performance of the catalyst for olefin polymerization of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer) (in the case of molecular weight, increasing the molecular weight), if necessary. used. Examples of such an organic compound include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

As the alcohols and the phenolic compound, those represented by R ^m- OH are usually used, where R ^m is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, a carbon atom). The number is 6 to 50) or the number of carbon atoms is 1 to 50 (in the case of phenols, the number of carbon atoms is 6 to 50).

Examples of the alcohols include those R ^m is a halogenated hydrocarbon group is preferable. Further, as the phenolic compound, those in which the α and α'-positions of the hydroxyl groups are replaced with hydrocarbons having 1 to 20 carbon atoms are preferable.

As the carboxylic acid, one represented by R ^n- COOH is usually used. R ⁿ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acids having a P—H bond, P—OR, phosphate having a P = O bond, and a phosphine oxide compound are preferably used.
Examples of the sulfonate include those represented by the following general formula (DA).

(In the general formula (Da), M ⁵ is an atom of Group 1 to 14 of the periodic table, and ^Ro is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. It is a hydrocarbon group, T is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7. U is an integer of 1 to 7, and tu ≧ 1.)

<Method for producing olefin polymer>
The method for producing an olefin polymer of the present invention is a method comprising a step of polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization described above, and preferably polymerizes or copolymerizes the olefin. The step of copolymerizing is a step of polymerizing ethylene alone or a step of copolymerizing ethylene with α-olefin having 3 or more and 20 or less carbon atoms. As described above, the term olefin in the present specification refers to any compound having a polymerizable double bond.

In the polymerization, the usage of each component constituting the catalyst of the present invention and the order of addition to the polymerizer are arbitrarily selected, and the following methods are exemplified.

(1) A method of adding the transition metal compound [A] alone to a polymerizer.

(2) A method of adding the transition metal compound [A] and the compound [B] to the polymerizer in an arbitrary order.

(3) A method of adding a catalyst component in which a transition metal compound [A] is supported on a carrier [C] and a compound [B] to a polymerizer in an arbitrary order.

(4) A method of adding a catalyst component in which compound [B] is supported on a carrier [C] and a transition metal compound [A] to a polymerizer in an arbitrary order.

(5) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] to a polymerizer.

(6) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and a compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.

(7) A method of adding a catalyst component in which compound [B] is supported on a carrier [C] and a transition metal compound [A] to a polymerizer in an arbitrary order.

(8) A method of adding a catalyst component in which compound [B] is supported on a carrier [C], a transition metal compound [A], and compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.

(9) A method in which a component in which the transition metal compound [A] is supported on the carrier [C] and a component in which the compound [B] is supported on the carrier [C] are added to the polymerizer in an arbitrary order.

(10) A method of adding a component in which the transition metal compound [A] is supported on the carrier [C], a component in which the compound [B] is supported on the carrier [C], and the compound [B] to an arbitrary order polymerizer. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.

(11) A method of adding a transition metal compound [A], a compound [B], and an organic compound component [D] to a polymerizer in an arbitrary order.

(12) A method of adding a component in which the compound [B] and the organic compound component [D] are previously brought into contact with each other, and the transition metal compound [A] to the polymerizer in an arbitrary order.

(13) A method of adding a component in which a compound [B] and an organic compound component [D] are supported on a carrier [C], and a transition metal compound [A] to a polymerizer in an arbitrary order.

(14) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are previously contacted, and an organic compound component [D] to a polymerizer in an arbitrary order.

(15) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are previously brought into contact with each other, and a compound [B] and an organic compound component [D] in an arbitrary order.

(16) The catalyst component in which the transition metal compound [A] and the compound [B] are previously contacted, and the component in which the compound [B] and the organic compound component [D] are previously contacted are added to the polymerizer in an arbitrary order. Method. In this case, the compound [B] that is brought into contact with the transition metal compound [A] and the compound [B] that is brought into contact with the organic compound component [D] may be the same or different.

(17) A method of adding a component in which a transition metal compound [A] is supported on a carrier [C], a compound [B], and an organic compound component [D] to a polymerizer in an arbitrary order.

(18) A method in which a component in which the transition metal compound [A] is supported on a carrier [C] and a component in which the compound [B] and the organic compound component [D] are previously contacted are added to the polymerizer in an arbitrary order.

(19) A method of adding a catalyst component in which a transition metal compound [A], a compound [B], and an organic compound component [D] are previously brought into contact with each other in an arbitrary order to a polymerizer.

(20) A method of adding a catalyst component in which a transition metal compound [A], a compound [B] and an organic compound component [D] are previously contacted, and a compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] that is brought into contact with the transition metal compound [A] and the organic compound component [D] and the compound [B] that is added alone may be the same or different.

(21) A method for adding a catalyst in which a transition metal compound [A], a compound [B], and an organic compound component [D] are supported on a carrier [C] to a polymerizer.

(22) A method of adding a catalyst component in which a transition metal compound [A], a compound [B], and an organic compound component [D] are supported on a carrier [C], and a component [B] to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.

An olefin is reserved for the solid catalyst component in which the transition metal compound [A] is supported on the carrier [C] and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C]. It may be polymerized, or the catalyst component may be further supported on the prepolymerized solid catalyst component.

In the present invention, the polymerization (single polymerization or copolymerization) can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, and the olefin itself to be subjected to polymerization. Can also be used as a solvent.

When polymerizing the olefin, the transition metal compound [A] is used in an amount of, for example, usually ^10-12 to ^10-2 mol, preferably ^10-10 to ^10-3 mol, per liter of the reaction volume. Be done.

The organometallic compound (B-1) is, for example, a molar ratio of the organometallic compound (B-1) to all the transition metal atoms (M) in the transition metal compound [A] [(B-1) / M]. Is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is the molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound [A] [(B-2). / M] is usually used in an amount such that it is 10 to 500,000, preferably 20 to 100,000. The compound (ionized ionic compound) (B-3) that reacts with the transition metal compound [A] to form an ion pair includes the ionized ionic compound (B-3) and the transition metal in the transition metal compound [A]. It is used in an amount such that the molar ratio to the atom (M) [(B-3) / M] is usually 1 to 10, preferably 1 to 5.

The organic compound component [D] has, for example, a molar ratio [[D] / (B-1)] with the organometallic compound (B-1) of usually 0.01 to 10, preferably 0.1 to 5. It is used in such an amount. The molar ratio [[D] / (B-2)] of the organic compound component [D] to the organoaluminum oxy compound (B-2) is usually 0.001-2, preferably 0.005-1. It is used in such an amount. The molar ratio [[D] / (B-3)] of the organic compound component [D] to the ionized ionic compound (B-3) is usually 0.01 to 10, preferably 0.1 to 5. It is used in such an amount.

The polymerization temperature is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually under normal pressure to 100 kg / cm ^2- G, preferably normal pressure to 50 kg / cm ^2- G, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Can also be done. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained polyolefin can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound [B] used.

The olefin that can be polymerized is not particularly limited as long as it has a polymerizable double bond, but is linear or branched having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms. Α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; the number of carbon atoms is 3 to 30, preferably 3 to 20, more preferably 3 to 10. Cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5, Examples thereof include 8,8a-octahydronaphthalene.

The catalyst for olefin polymerization of the present invention can be used for homopolymerization of ethylene or copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. It is more preferable to use it. One type of α-olefin may be used alone, or two or more types may be used in combination.

In the case of copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter, also referred to as olefin A) is particularly effective as long as the effect of the present invention is exhibited. For example, but not limited to, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1- Desen is preferred. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferable.

When ethylene is used and the olefin A is used, the usage ratio of ethylene to the olefin A is ethylene: the olefin A (molar ratio), usually 1: 10 to 5000: 1, preferably 1: 5 to 5. 1000: 1.

The olefin polymerization catalyst of the present invention may be used to polymerize a chain unsaturated hydrocarbon having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.). As this unsaturated hydrocarbon, for example

Acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12- Tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henkocenoic acid, 21-dococenoic acid, 22- Tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2,6- Heptadylic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- (10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1]-5-heptene-2 -Carboxylic acids, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and their sodium, potassium, lithium, zinc, magnesium and calcium salts. Metal salts such as, and unsaturated carboxylic acids such as methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester of these unsaturated carboxylic acids. Esters (which may be monoesters or diesters if the unsaturated carboxylic acid is a dicarboxylic acid) and unsaturated carboxylic acids such as amides, N, N-dimethylamides of these unsaturated carboxylic acids. Acid amides (may be monoamides or diamides if the unsaturated carboxylic acid is a dicarboxylic acid);

Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] ] -Saturated carboxylic acid anhydrides such as 5-heptene-2,3-dicarboxylic acid anhydride;

Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caproate, vinyl laurate, vinyl stearate;

Allyl esters such as allyl acetate, allyl propionate, allyl caproate, allyl caprate, allyl laurate, allyl stearate;

Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;

Halogenated styrenes such as o-chlorostyrene and p-chlorostyrene;

Cyrilized olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, and allyltriphenylsilane;

Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5-heptene;

Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenor, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol , And these unsaturated esters such as acetate, benzoic acid ester, propionic acid ester, caproic acid ester, capric acid ester, lauric acid ester, stearic acid ester;

Substituted phenols such as vinylphenol and allylphenol, and unsaturated esters such as acetic acid ester, benzoic acid ester, propionic acid ester, caproic acid ester, capric acid ester, lauric acid ester and stearic acid ester;

Substituted benzyl alcohols such as vinylbenzyl alcohol and allylbenzyl alcohol, and unsaturated esters such as acetic acid esters, benzoic acid esters, propionic acid esters, caproic acid esters, capric acid esters, lauric acid esters and stearic acid esters;

Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl metalyl ether, methoxystyrene, ethoxystyrene, allyl anisole;

Unsaturated epoxides such as butadiene monooxide, 1,2-epoxy-7-octene, 3-vinyl7-oxabicyclo [4.1.0] heptane;

Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;

Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and unsaturated acetals such as these dimethyl acetals and diethyl acetals;

Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;

Unsaturated sulfoxides such as allylphenyl sulfoxide;

Unsaturated sulfones such as allylphenyl sulfone;

Unsaturated phosphines such as allyldiphenylphosphine;

Unsaturated phosphine oxides such as allyldiphenylphosphine oxides; and the like.

Further, unsaturated hydrocarbons having two or more of the above-mentioned polar groups, such as vinyl trifluoroacetate, allyl trifluoroacetate, methyl 4- (3-butenyloxy) benzoate, glycidyl acrylate, allyl glycidyl ether, (2H-Perfluoropropyl) -2-propenyl ether, linalol oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholin, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, Acrylic trimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane and the like may also be polymerized using the olefin polymerization catalyst of the present invention.

Further, the catalyst for olefin polymerization of the present invention may be used to polymerize vinylcyclohexane, diene, polyene and the like.

Examples of the diene or the polyene include cyclic or chain compounds having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. In particular,

Butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadien, 1,4-Octadiene, 1,5-octadien, 1,6-octadien, 1,7-octadien, etylidene norbornene, vinyl norbornene, dicyclopentadiene;

7-Methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien;

Further, mono or poly such as aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. Alkylstyrene;

Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;

Examples thereof include 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene; and the like.

<Olefin polymer>
According to the present invention, in the presence of an olefin polymerization catalyst containing a useful and novel transition metal compound [A] having the above-mentioned specific structure, one or more α-alphas having 2 to 30 carbon atoms By polymerizing an olefin; preferably by homopolymerizing ethylene, or by copolymerizing ethylene with at least one olefin A selected from α-olefins having 3 to 20 carbon atoms. Can be efficiently manufactured.

As one aspect of the olefin polymer, an ethylene-based polymer containing an ethylene-derived structural unit in the range of preferably 90 to 100 mol%, more preferably 92 to 100 mol%, still more preferably 95 to 100 mol% can be mentioned. Be done. The ethylene polymer contains the structural units derived from the olefin A in a total range of 0 to 10 mol%, more preferably 0 to 8 mol%, and further preferably 0 to 5 mol%. However, the total of the content of the structural unit derived from ethylene and the content of the structural unit derived from olefin A is 100 mol%. The ethylene-based polymer whose constituent unit derived from olefin A is in the above range is excellent in moldability. Further, other constituent units may be included as long as the gist of the present invention is not deviated. These contents can be measured by nuclear magnetic resonance spectroscopy, infrared spectroscopy when there is a reference substance, or the like.

Among these polymers, ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene polymer, ethylene / 1 -Hexen polymer, ethylene / 4-methyl-1-pentene polymer, ethylene / propylene / 1-octene polymer, ethylene / propylene / 1-hexene polymer, ethylene / propylene / 4-methyl-1-pentene polymer Is particularly preferable. Further, it may be a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more kinds selected from these polymers.

Among the polymers having the structural units described above, the ethylene-based polymer is preferably an α-olefin polymer consisting of only the structural units derived from α-olefins having 2 to 20 carbon atoms. “Substantially” means that the ratio of the constituent units derived from α-olefin having 2 to 20 carbon atoms to all the constituent units is 95% by weight or more.

In the olefin polymer, the weight average molecular weight measured by the gel permeation chromatography (GPC) method is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000 to 2, It is ,000,000, particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 30, more preferably 1 to 15, and particularly preferably 1 to 1. It is 10. The molecular weight distribution can also be adjusted by producing polymers having different molecular weights by a multi-stage polymerization method or the like, or by a method such as solvent separation.

In the olefin polymer, the density is not particularly limited, it is preferably not more than 875kg / ^{m 3} or more 975 kg / ^{m 3.}

In the olefin polymer, the ultimate viscosity [η] in the 135 ° C. decalin is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 dl / g, and particularly preferably 1 to 10 dl / g. g.

In the olefin polymer, the melt mass flow rate (MFR; unit is g / 10 minutes) measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, but is preferably 0.001 g /. It is 10 minutes or more and 300 g / 10 minutes or less, more preferably 0.001 g / 10 minutes or more and 200 g / 10 minutes or less.

Further, according to ASTM D1238-89, the value (I10 / I2) obtained by dividing the MFR value measured under the condition of 190 ° C. and 10 kg load by the MFR value measured under the condition of 190 ° C. and 2.16 kg load is 6 It is preferably .0 or more and less than 300.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the description of the following examples.

The transition metal compounds synthesized in each example. 270MHz, ¹ H-NMR (JEOL; GSH-270), Gas Chromatograph Mass Spectrometer (GC-MS) (Shimadzu Seisakusho; GCMS-QP5050A and Shimadzu Seisakusho; GCMS-QP2010 Ultra), FD-Mass Spectrometry (JEOL SX- It was identified using 102A).

<(1) Synthesis of transition metal compounds>
[Example 1]
1.89 g (20.1 mmol) of 1,3-dimethylcyclopentadiene and 40 mL of tetrahydrofuran were placed in a 200 mL reactor that had been sufficiently dried and substituted with argon, and 13.0 mL of n-butyllithium solution (hexane solution, 1.63 M, 21.2 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This suspension was slowly added to 12.0 mL (100 mmol) of dimethylsilyldichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 2.00 mL (21.3 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 10.4 g (tetrahydrofuran solution, 25 wt%, 21.3 mmol) of n-butylcyclopentadiene solution and 20 mL of tetrahydrofuran were placed in a 200 mL reactor that had been sufficiently dried and substituted with argon, and 13.0 mL of n-butyllithium solution (hexane solution) was charged. (1.63 M, 21.2 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. When the residue obtained by distilling off the filtrate after filtering magnesium sulfate is purified by silica gel column chromatography, 1.82 g (yield 33) of the compound (1a) represented by the following formula (1a) is obtained. %) Was obtained as a mixture of isomers.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.76-5.00 (5H, m), 3.50-2.52 (2H, m), 2.50-2.22 (2H, m), 2 .22-1.10 (10H, m), 1.00-0.78 (3H, m), -0.21 (6H, s, Si-CH ₃ ) ppm

1.49 g (5.45 mmol) of the compound (1a) obtained in the above step, 20 mL of toluene, and 0.9 mL of tetrahydrofuran were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 6.70 mL of an n-butyllithium solution (hexane solution, 1.63 M, 10.9 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 20 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 0.65 mL (5.44 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to find 1.33 g of the target product (hereinafter referred to as compound (1b)) represented by the following formula (1b). It was obtained as an isomer mixture (yield 74%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.81 (1H, s, C = CH-C), 6.38 (1H, s, C = CH-C), 6.08 (1H, s, C = CH-C), 3.45 (1H, s, Si-CH), 3.17 (1H, d, J = 1.6Hz, Si-CH), 2.43 (2H, t, J = 1.6Hz) _{, -CH 2 -C 3 H 7)} , 2.22-1.93 (6H, m, C-CH 3), 1.72-1.15 (4H, m, -CH 2 -C 2 H 4 - _{CH 3), 0.93 (3H,} t, J = 7.2Hz, -C 3 H 6 -CH 3), 0.64-0.30 (6H, m, Si-CH 3), - 0.40 (3H, s, Si-CH ₃ ), -0.52 (3H, s, Si-CH ₃ ) ppm

0.33 g (1.01 mmol) of the ligand compound (1b) obtained in the above step, 10 mL of toluene, and 0.17 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 1.25 mL of an n-butyllithium solution (hexane solution, 1.63 M, 2.04 mmol) was added at room temperature, and then stirring was continued for 4 hours in an oil bath at 40 ° C. After distilling off the solvent, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.23 g (1.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding n-hexane to the obtained solid, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure as described below. 0.28 g (27% yield) of a white powdery compound represented by the formula (1) (hereinafter referred to as metallocene compound (1)) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.54 (2H, s, Cp-H), 6.02 (1H, s, Cp-H), 2.69 (2H, t, J = 7.3 Hz, Cp-CH _2- ), 2.19 (6H, s, Cp-CH ₃ ), 1.70-1.55 (2H, m, -CH _2- ), 1.46-1.28 (2H, m) _{, -CH 2 -), 0.92 (} 3H, t, J = 7.3Hz, -C 3 H 6 -CH 3), 0.85 (6H, s, Si-CH 3), 0.54 (6H , S, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 488

[Example 2]
2.11 g (9.15 mmol) of (3-n-propylcyclopentadienyl) (cyclopentadienyl) dimethylsilane synthesized by the method described in Japanese Patent No. 5455354 in a 100 mL reactor sufficiently dried and substituted with argon. ), 30 mL of toluene and 1.50 mL of tetrahydrofuran were charged and stirred. After adding 11.3 mL of an n-butyllithium solution (hexane solution, 1.63 M, 18.4 mmol) to this solution at room temperature, stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 30 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 2.20 mL (18.4 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to find 1.96 g of the target product represented by the following formula (2a) (hereinafter referred to as compound (2a)). It was obtained as an isomer mixture (yield 75%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.23-6.24 (5H, m, C = CH-C), 3.54 (1H, d, J = 5.0 Hz, Si-CH), 3. 36 (1H, d, J = 9.8Hz, Si-CH), 2.55-2.30 (2H, m, -CH 2 -C 2 H 5), 1.66-1.52 (2H, m _{, -CH 2 -CH 2 -CH 3)} , 0.96 (3H, t, J = 7.1Hz, -C 2 H 4 -CH 3), 0.58-0.42 (6H, m, Si- CH ₃ ), -0.44 (3H, d, J = 6.7Hz, Si-CH ₃ ), -0.51 (3H, d, J = 4.9Hz, Si-CH ₃ ) ppm

1.96 g (6.85 mmol) of the ligand compound (2a) obtained in the above step, 30 mL of toluene, and 1.20 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution was added 8.40 mL of an n-butyllithium solution (hexane solution, 1.63 M, 13.7 mmol) at room temperature, followed by stirring in an oil bath at 40 ° C. for 4 hours. After distilling off the solvent, 30 mL of hexane was added to the obtained solid to prepare a suspension, the insoluble material was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 1.77 g of a lithium product. .. Diethyl ether (10 mL) was added to 0.30 g (1.00 mmol) of this lithiated product to prepare a suspension, which was cooled to 0 ° C., 0.23 g (1.00 mmol) of zirconium tetrachloride was added, and the mixture was stirred at room temperature for 72 hours. Continued. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding toluene and n-hexane to the obtained solid, and the insoluble material was filtered off by a glass filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding n-hexane to the obtained solid, and the insoluble material was filtered off with a glass filter. After distilling off the solvent of the obtained solution, the residue was dried under reduced pressure to obtain a compound represented by the following formula (2) (hereinafter referred to as metallocene compound (2)) as a crude product.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.93 (2H, d, J = 2.6 Hz, Cp-H), 6.65 (2H, s, Cp-H), 6.52-6.47 ( 1H, m, Cp-H), 2.63 (2H, t, J = 7.7Hz, Cp-CH _2- ), 1.75-1.55 (2H, m, -CH _2- ), 1. _{00-0.87 (9H, m, -C 2} H 4 -CH 3 & Si-CH 3), 0.52 (6H, s, Si-CH 3) ppm
FD-Mass Spectrometry (M ⁺ ): 446

[Example 3]
12.0 mL (100 mmol) of dimethylsilyldichloride and 10 mL of n-hexane were placed in a 200 mL reactor that had been thoroughly dried and replaced with argon, and 40.0 mL of sodium cyclopentadiene solution (tetrahydrofuran solution, 0.50 M, 20.0 mmol) was charged. ) Was slowly added under cooling at −78 ° C., and the mixture was stirred at room temperature for 20 hours. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 2.00 mL (21.3 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 2.73 g (20.0 mmol) of 1-n-butyl-3-methylcyclopentadiene and 20 mL of tetrahydrofuran were placed in a 200 mL reactor that had been sufficiently dried and substituted with argon, and 12.3 mL of an n-butyllithium solution (hexane solution, 1.63 M, 20.0 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 19 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of the magnesium sulfate and the residue obtained by evaporating the filtrate purified by silica gel column chromatography, the desired product represented by the following formula (3 a) (hereinafter referred to as the compound (3a)) is 1. It was obtained as a 23 g (24% yield) isomer mixture.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.00-6.00 (6H, m), 3.60-2.80 (2H, m), 2.50-2.22 (2H, m), 2 .22-1.90 (2H, m), 1.51-1.20 (5H, m), 1.00-0.80 (6H, m), 0.20-0.40 (6H, m) ) Ppm

1.23 g (4.74 mmol) of the compound (3a) obtained in the above step, 30 mL of toluene, and 0.8 mL of tetrahydrofuran were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 5.82 mL of an n-butyllithium solution (hexane solution, 1.63 M, 9.49 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 30 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 0.57 mL (4.75 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of the magnesium sulfate and the residue obtained by evaporating the filtrate purified by silica gel column chromatography, the desired product (hereinafter Compound (3b) hereinafter) represented by the following formula (3b) is 0.91g It was obtained as an isomer mixture (yield 68%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.02-6.00 (4H, m, C = CH-C), 3.62 (1H, s, Si-CH), 3.24 (1H, s, _{Si-CH), 2.55-2.25 (2H} , m, -CH 2 -C 3 H 7), 2.21-2.01 (3H, m, C-CH 3), 1.47-1 _{.23 (4H, m, -CH 2} -C 2 H 4 -CH 3), 0.93 (3H, t, J = 7.3Hz, -C 3 H 6 -CH 3), 0.68-0. 25 (6H, m, Si-CH ₃ ), -0.35-0.45 (3H, s, Si-CH ₃ ), -0.55 (3H, s, Si-CH ₃ ) ppm

0.32 g (1.00 mmol) of the ligand compound (3b) obtained in the above step, 10 mL of toluene, and 0.17 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 1.25 mL of an n-butyllithium solution (hexane solution, 1.63 M, 2.04 mmol) was added at room temperature, and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to −78 ° C., 0.23 g (1.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding toluene and n-hexane to the obtained solid, and the insoluble material was filtered off by a glass filter. After distilling off the solvent of the obtained solution, a suspension was prepared by adding n-hexane to the obtained solid, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure as described below. 0.11 g (23% yield) of a white powdery compound represented by the formula (3) (hereinafter referred to as metallocene compound (3)) was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 6.85 (2H, d, J = 2.6 Hz, Cp-H), 6.53 (1H, t, J = 2.8 Hz, Cp-H), 6. 05 (1H, s, Cp-H), 2.73-2.58 (1H, m, Cp-CH _2- ), 2.40-2.24 (1H, m, Cp-CH _2- ), 2 _{.20 (3H, s, Cp-} CH 3), 1.60-1.20 (4H, m, -C 2 H 4 -), 0.90 (3H, t, J = 6.9Hz, -C 3 H _6- CH ₃ ), 0.87 (6H, s, Si-CH ₃ ), 0.58 (3H, s, Si-CH ₃ ), 0.57 (3H, s, Si-CH ₃ ) ppm
FD-Mass Spectrometry (M ⁺ ): 474

[Example 4]
2.02 g (83.1 mmol) of magnesium pieces were charged into a 200 mL reactor that had been sufficiently dried and replaced with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 25 mL of tetrahydrofuran were charged and stirred. A 20 mL diluted solution of 3-92 g (20.1 mmol) of 2-bromoinden in tetrahydrofuran was slowly added, and the mixture was heated under reflux in an oil bath at 80 ° C. for 1 hour. This reaction solution was slowly added to 12.0 mL (100 mmol) of dimethylsilyldichloride in 10 mL of n-hexane under cooling at −78 ° C., and stirring was continued for 18 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyldichloride, 20 mL of tetrahydrofuran and 1.90 mL (20.2 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. 9.79 g (tetrahydrofuran solution, 25 wt%, 20.0 mmol) of n-butylcyclopentadiene solution and 20 mL of tetrahydrofuran were placed in a 100 mL reactor that had been sufficiently dried and substituted with argon, and 12.5 mL of n-butyllithium solution (hexane solution) was charged. 1.60 M, 20.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the reaction residue diluted solution cooled to −78 ° C., and stirring was continued for 17 hours while slowly returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off and the obtained residue was purified by silica gel column chromatography to find 4.65 g of the target product represented by the following formula (4a) (hereinafter referred to as compound (4a)). It was obtained as an isomer mixture (yield 79%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.52-7.35 (2H, m, Ar-H), 7.32-7.08 (3H, m, Ar-H & C = CH-C), 7. 02-5.70 (3H, m, C = CH-C), 3.60-2.87 (3H, m, Ar-CH _2- C & Si-CH), 2.39 (2H, t, J = 7) _{.7Hz, -CH 2 -C 3 H 7} ), 1.59-1.41 (2H, m, -CH 2 -), 1.41-1.20 (2H, m, -CH 2 -), 0 _{.87 (3H, t, J =} 7.2Hz, -C 3 H 6 -CH 3), 0.50-0.02 (6H, m, Si-CH 3) ppm

3.83 g (13.0 mmol) of the compound (4a) obtained in the above step, 50 mL of toluene and 2.2 mL of tetrahydrofuran were charged into a 200 mL reactor that had been sufficiently dried and substituted with argon, and stirred. 16.3 mL of n-butyllithium solution (hexane solution, 1.60 M, 26.1 mmol) was added to this solution under cooling at 0 ° C., and then stirring was continued for 3 hours in an oil bath at 40 ° C. After distilling off the solvent, 50 mL of tetrahydrofuran was added to the obtained solid. The solution was cooled to −78 ° C., 1.55 mL (13.0 mmol) of dimethylsilyldichloride was added, and stirring was continued for 17 hours while returning to room temperature. A saturated aqueous solution of ammonium chloride was added, the soluble component was extracted with n-hexane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to find 3.55 g of the target product (hereinafter referred to as compound (4b)) represented by the following formula (4b). It was obtained as an isomer mixture (yield 78%).

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.48 (2H, t, J = 7.3 Hz, Ar-H), 7.30-7.13 (3H, m, Ar-H & C = CH-C), 6.90 (1H, s, C = CH-C), 6.43 (1H, s, C = CH-C), 3.91-3.37 (2H, m, Ar-CH _2- C & Si-CH) _{), 2.47 (2H, t,} J = 7.9Hz, -CH 2 -C 3 H 7), 1.67-1.49 (2H, m, -CH 2 -), 1.49-1. _{22 (2H, m, -CH 2} -), 0.95 (3H, t, J = 7.2Hz, -C 3 H 6 -CH 3), 0.63 (3H, s, Si-CH 3), 0.59 (3H, s, Si-CH ₃ ), -0.42 (3H, s, Si-CH ₃ ), -0.75 (3H, s, Si-CH ₃ ) ppm

0.35 g (1.01 mmol) of the ligand compound (4b) obtained in the above step, 10 mL of toluene, and 0.17 mL of tetrahydrofuran were charged into a 100 mL reactor that had been sufficiently dried and substituted with argon, and stirred. To this solution, 1.25 mL of an n-butyllithium solution (hexane solution, 1.60 M, 2.00 mmol) was added at room temperature, and then stirring was continued for 4 hours in an oil bath at 40 ° C. After distilling off the solvent, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.23 g (1.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to be represented by the following formula (4). 0.17 g (yield 34%) of the compound (hereinafter referred to as metallocene compound (4)) in the form of a pale yellow powder was obtained.

^{1 1} H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1 H, dt, J = 1.1 and 8.3 Hz, Ar-H), 7.37-7.19 (3 H, m, Ar-H), 7. 13 (1H, d, J = 0.7Hz, Cp-H), 6.23 (1H, d, J = 1.6Hz, Cp-H), 6.41 (1H, d, J = 01.7Hz, Cp-H), 2.55 (2H, t, J = 7.6Hz, Cp-CH _2- ), 1.65-1.47 (2H, m, -CH _2- ), 1.40-1. 22 (2H, m, -CH _2- ), 1.02 (3H, s, Si-CH ₃ ), 0.96 (3H, s, Si-CH ₃ ), 0.88 (3H, t, J = _{7.3Hz, -C 3 H 6 -CH 3} ), 0.73 (3H, s, Si-CH 3), 0.60 (3H, s, Si-CH 3) ppm
FD-Mass Spectrometry (M ⁺ ): 510

[Comparative Example 1]
(1,1'-dimethylsilylene) (2,2'-dimethylsilylene)-(cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride (hereinafter referred to as metallocene) represented by the following formula (5). Compound (5)) was synthesized according to the method described in WO 2002/092641.

[Comparative Example 2]
(1,1'-dimethylsilylene) (2,2'-dimethylsilylene)-(3', 5'-cyclopentadienyl) (3,5-dimethylcyclopentadienyl) represented by the following formula (6) ) Zirconium dichloride (hereinafter referred to as metallocene compound (6)) was synthesized according to the method described in JP-A-2003-105016.

<(2) Preparation of solid carrier>
Using a reactor with an internal volume of 270 L, silica gel (manufactured by Fuji Silysia Chemical Ltd .: cumulative 50% particle size 70 μm, specific surface area 340 m ² / g, pore volume of volume distribution by laser light diffraction scattering method) (1.3 cm ³ / g, dried at 250 ° C. for 10 hours) 10 kg was suspended in 77 L of toluene and then cooled to 0-5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C.

Then, after contacting at 0 to 5 ° C. for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and then contact was continued at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry of a solid carrier having a total volume of 115 liters.

When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 122.6 g / L.

<(3) Preparation of solid catalyst component for olefin polymerization>
[Example 5]
30 mL of toluene and 8.2 mL of the above solid-state carrier slurry (solid weight: 1.0 g) were charged into a reactor with a stirrer having an internal volume of 200 mL that was sufficiently nitrogen-substituted. Next, a 0.025 mmol toluene solution of the metallocene compound (1) obtained in Example 1 was added, and the mixture was contacted at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and heptane was further added. After washing twice using the mixture, a slurry of the solid catalyst component (I) for olefin polymerization having a total volume of 50 ml was prepared.

[Examples 6 to 8]
Solid catalyst component for olefin polymerization (II) in the same manner as in Example 5 except that the metallocene compounds (2) to (4) obtained in Examples 2 to 4 were used instead of the metallocene compound (1). -(IV) slurry was prepared.

[Comparative Examples 3 to 4]
The solid catalyst component (V) for olefin polymerization was used in the same manner as in Example 5 except that the metallocene compounds (5) to (6) obtained in Comparative Examples 1 and 2 were used instead of the metallocene compound (1). ~ (VI) slurry was prepared.

<(4) Olefin polymerization>
[Example 9]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L sufficiently nitrogen-substituted, ethylene was substituted in the system, and then 0.375 mmol of triisobutylaluminum and the solid catalyst component (I) obtained in Example 5 were added. 80 mg was added as a solid content, and the temperature in the system was raised to 80 ° C. Then, ethylene was continuously introduced to carry out a polymerization reaction at a total pressure of 0.8 MPaG and 80 ° C. for 90 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 18.8 g of an ethylene polymer. The polymerization activity was 9744 g-PE / mmol-Zr.

[Example 10]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L sufficiently nitrogen-substituted, ethylene was substituted in the system, and then 0.375 mmol of triisobutylaluminum and the solid catalyst component (I) obtained in Example 5 were added. 100 mg was added as a solid content, and the temperature in the system was raised to 80 ° C. Next, a hydrogen / ethylene mixed gas (hydrogen concentration 0.10 vol%) was continuously introduced to carry out a polymerization reaction at a total pressure of 0.8 MPaG and 80 ° C. for 90 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 19.5 g of an ethylene polymer. The polymerization activity was 8060 g-PE / mmol-Zr.

The obtained polymer was measured according to ASTMD1238-65T at 190 ° C. under the condition of 2.16 kg weighting, and the melt flow rate (MFR) value (I ₂ ) was 0.35 g / 10 minutes under the condition of 10 kg weighting. The measured value (I ₁₀ ) was 3.03 g / 10 minutes, and the ratio of the two (I ₁₀ / I ₂ ) was 8.66.

[Example 11]
500 mL of heptane was charged into a stainless steel autoclave having an internal volume of 1 L sufficiently nitrogen-substituted, and after ethylene-substituted in the system, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum and the solid obtained in Example 5 above 16 mg of the catalyst component (I) was added as a solid content, and the temperature in the system was raised to 80 ° C. Then, ethylene was continuously introduced to carry out a polymerization reaction at a total pressure of 0.8 MPaG and 80 ° C. for 90 minutes. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 5.07 g of an ethylene polymer. The polymerization activity was 13118 g-PE / mmol-Zr.

[Examples 12 to 14]
The same method as in Examples 9 to 11 except that the solid catalyst component (II) obtained in Example 6 was used instead of the solid catalyst component (I) (however, the amount of the solid catalyst component in Example 9 was The polymerization reaction was carried out with (changed to 100 mg).

The ethylene polymer obtained in Example 12 was 18.8 g, and the polymerization activity was 11896 g-PE / mmol-Zr. The ethylene polymer obtained in Example 13 was 31.3 g, the polymerization activity was 12753 g-PE / mmol-Zr, (I ₂ ) was 2.06 g / 10 minutes, and (I ₁₀ ) was 15.24 g. At / 10 minutes, (I ₁₀ / I ₂ ) was 7.39. The ethylene polymer obtained in Example 14 was 42.7 g, and the polymerization activity was 17405 g-PE / mmol-Zr.

[Examples 15 to 17]
The same method as in Examples 9 to 11 except that the solid catalyst component (III) obtained in Example 7 was used instead of the solid catalyst component (I) (however, the amount of the solid catalyst component in Example 9 was The polymerization reaction was carried out with (changed to 100 mg).

The ethylene polymer obtained in Example 15 was 50.3 g, and the polymerization activity was 20521 g-PE / mmol-Zr. The ethylene polymer obtained in Example 16 was 30.4 g, the polymerization activity was 12414 g-PE / mmol-Zr, (I ₂ ) was 0.33 g / 10 minutes, and (I ₁₀ ) was 2.20 g. At / 10 minutes, (I ₁₀ / I ₂ ) was 6.71. The ethylene polymer obtained in Example 17 was 24.2 g, and the polymerization activity was 9895 g-PE / mmol-Zr.

[Examples 18 to 20]
The same method as in Examples 9 to 11 except that the solid catalyst component (IV) obtained in Example 8 was used instead of the solid catalyst component (I) (however, the amount of the solid catalyst component in Example 9 is The polymerization reaction was carried out with (changed to 100 mg).

The ethylene polymer obtained in Example 18 was 25.8 g, and the polymerization activity was 10553 g-PE / mmol-Zr. The ethylene polymer obtained in Example 19 was 28.5 g, the polymerization activity was 11632 g-PE / mmol-Zr, (I ₂ ) was 0.56 g / 10 minutes, and (I ₁₀ ) was 8.49 g. At / 10 minutes, (I ₁₀ / I ₂ ) was 15.28. The ethylene polymer obtained in Example 20 was 65.4 g, and the polymerization activity was 26715 g-PE / mmol-Zr.

[Comparative Examples 5 to 7]
The same method as in Examples 9 to 11 except that the solid catalyst component (V) obtained in Comparative Example 3 was used instead of the solid catalyst component (I) (however, the amount of the solid catalyst component in Example 9 was The polymerization reaction was carried out with (changed to 100 mg).

The ethylene polymer obtained in Comparative Example 5 was 6.09 g, and the polymerization activity was 2491 g-PE / mmol-Zr. The ethylene polymer obtained in Comparative Example 6 was 9.87 g, the polymerization activity was 2523 g-PE / mmol-Zr, (I ₂ ) was 0.22 g / 10 minutes, and (I ₁₀ ) was 2.02 g. At / 10 minutes, (I ₁₀ / I ₂ ) was 9.20. The ethylene polymer obtained in Comparative Example 7 was 1.78 g, and the polymerization activity was 3641 g-PE / mmol-Zr.

[Comparative Examples 8 to 10]
The same method as in Examples 9 to 11 except that the solid catalyst component (VI) obtained in Comparative Example 4 was used instead of the solid catalyst component (I) (however, the amount of the solid catalyst component in Example 9 was The polymerization reaction was carried out with (changed to 100 mg).

The ethylene polymer obtained in Comparative Example 8 was 8.51 g, and the polymerization activity was 3483 g-PE / mmol-Zr. The ethylene polymer obtained in Comparative Example 9 was 12.0 g, the polymerization activity was 4100 g-PE / mmol-Zr, (I ₂ ) was 0.15 g / 10 minutes, and (I ₁₀ ) was 1.35 g. At / 10 minutes, (I ₁₀ / I ₂ ) was 9.00. The ethylene polymer obtained in Comparative Example 9 was 2.28 g, and the polymerization activity was 2333 g-PE / mmol-Zr.

The results of Examples 9 to 20 and Comparative Examples 5 to 10 are summarized in Table 7.

As shown in Table 7, the metallocene compounds (1) to (4) of Examples 1 to 4 were used in comparison with the polymerization reaction of Comparative Examples 5 to 10 using known metallocene compounds (5) and (6). In the polymerization reactions of Examples 9 to 20, a significant improvement in polymerization activity was observed under all the polymerization conditions.

Furthermore, in Examples 10, 13, 16 and 19, the value of (I ₁₀ / I ₂ ) did not fall below 6.00. The fact that the value of (I ₁₀ / I ₂ ) is less than 6.00 means that there is substantially no long-chain branching (LCB). Further, Example 19 has a higher value than Comparative Examples 6 and 9 _(I 10 / I _2), Examples 10, 13 and 16 values than Comparative Examples 6 and 9 _(I 10 / I ₂₎ It is a little low, but it is about the same level. That is, it was found that in Examples 10, 13, 16 and 19, the amount of long chain branch (LCB) introduced was maintained at almost the same level as in Comparative Examples 6 and 9 .

By using a catalyst for olefin polymerization containing a novel transition metal compound having a specific substituent of the present invention introduced, for example, when ethylene is homopolymerized or ethylene and α-olefin are copolymerized, it is contained in polyethylene. The olefin polymerization activity can be improved without significantly reducing the LCB level of. According to the present invention, it is expected that a polyolefin having an excellent balance of impact resistance, light weight, transparency and processability, which makes the best use of these characteristics, can be provided with high productivity. Therefore, it can be said that the present invention has extremely high industrial value.

Claims (14)

A transition metal compound represented by the following general formula [4] .

(In the general formula [4] ,
M is a zirconium atom
n is an integer of 1 to 4 that satisfies the valence of M.
X is a halogen atom
Q ³ and ^{Q 4} is a silicon atom,
R ^{7 to} R ¹⁰ are hydrogen atoms, methyl groups, ethyl groups, isopropyl groups or butyl groups, which may be the same or different from each other.
R ^{1 to} R ⁶ are hydrogen atoms and hydrocarbon groups having 1 to 4 carbon atoms , and may be the same or different from each other.
R ⁵ and R ⁶ may combine to form a benzene ring that condenses with the cyclopentadienyl ring, whereby the entire ring structure with R ^{4 to} R ⁶ may form an indene skeleton.
However, at least one of R ^{1 to} R ⁶ is a substituent represented by the following general formula [2] or a substituent represented by the following general formula [3]. )

(In the general formulas [2] and [3], m is 1 or 2. ) Of R ^{1 to} R ⁶ , 1 to 3 groups are hydrocarbon groups having 1 to 4 carbon atoms, which may be the same or different from each other, and the remaining 3 to 5 groups are hydrogen atoms. Yes,
R ⁵ and R ⁶ may combine to form a benzene ring that condenses with the cyclopentadienyl ring, whereby the entire ring structure with R ^{4 to} R ⁶ may form an indene skeleton.
The transition metal compound according to claim 1, wherein at least one of the hydrocarbon groups having 1 to 4 carbon atoms is a group represented by the general formula [2] or the general formula [3] . The transition metal compound according to claim 1 or 2 , wherein the hydrocarbon group as R ^{1 to} R ⁶ is an alkyl group having 1 to 4 carbon atoms or a substituent represented by the general formula [3] . One group of R ^{1 to} R ⁶ is a substituent represented by the general formula [2] or the general formula [3], and two groups are a methyl group or a hydrogen atom. The two groups may be the same or different, and the three groups are hydrogen atoms.
R ⁵ and R ⁶ may combine to form a benzene ring that condenses with the cyclopentadienyl ring, whereby the entire ring structure with R ^{4 to} R ⁶ may form an indene skeleton.
The transition metal compound according to claim 2 . Of R ^{1 to} R ⁶ , one group is a substituent represented by the general formula [2], two groups are a methyl group or a hydrogen atom, and the two groups are the same. But it can be different, the three groups are hydrogen atoms,
R ⁵ and R ⁶ may combine to form a benzene ring that condenses with a cyclopentadienyl ring, whereby the entire ring structure with R ^{4 to} R ⁶ may form an indene skeleton. Item 2. The transition metal compound according to Item 2 . R ¹ , R ³ and R ⁵ are hydrogen atoms,
R ² is a hydrogen atom, n-propyl group or n-butyl group,
R ⁴ is a hydrogen atom or a methyl group,
R ⁶ is a hydrogen atom, a methyl group, an n-propyl group or an n-butyl group.
R ⁵ and R ⁶ may combine to form a benzene ring that condenses with a cyclopentadienyl ring, whereby the entire ring structure with R ^{4 to} R ⁶ may form an indene skeleton. Item 5. The transition metal compound according to Item 5 . R ^7- Q ^3- R ⁸ and R ^9- Q ^4- R ¹⁰ are silylene, methyl silylene, dimethyl silylene, diethyl silylene, diisopropyl silylene, dibutyl silylene, methylbutyl silylene or methyl-t-butyl silylene, and each other. The transition metal compound according to any one of claims 1 to 6, which may be the same or different . The transition metal compound according to any one of claims 1 to 6 , wherein R ⁷ and R ⁸ are the same group, and R ⁹ and R ¹⁰ are the same group. The transition metal compound according to claim 7 , wherein R ^7- Q ^3- R ⁸ and R ^9- Q ^4- R ¹⁰ are the same group. The transition metal compound according to claim 9, which is any one of the compounds represented by the following formulas (1) to (4).

A catalyst for olefin polymerization, which comprises the transition metal compound [A] according to any one of claims 1 to 10 . further,
[B] (B-1) Organometallic compound,
11. Claim 11 contains at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. Olefin polymerization catalyst. A method for producing an olefin polymer, which comprises a step of polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 11 or 12 . The method for producing an olefin polymer according to claim 13 , wherein the step of polymerizing or copolymerizing an olefin is a step of polymerizing ethylene alone or a step of copolymerizing ethylene with an α-olefin having 3 or more and 20 or less carbon atoms.